Silver hal



Jan. 24, 1956 s. RICHMAN ETAL 2,732,305

ANTI-HALATION LAYERS CONTAINING FATTY ACID AMIDES Filed Nov. 7. 1950 SILVER HAL/D5 E/l/Z/LS/O/V F/LM BASE ALKAL/ SOLK/EZE A/V77-HAL/J770V LAMS? CO/VTA/N/IVG /1 FA 777 40/0 AM/DE 0F FROM 8 70/8 CHRBO/V 1470445 SEYMOUR RIC/{MAN RUSSEL F. 14572? INVENTORS ATTORNEYS United States Patent ANTI-HALATION LAYERS CONTAINING FATTY ACID AMIDES Seymour Richman and Russell P. Easton, Binghamton,

N. Y., assignors to General Aniline & Fiim Corporation, New York, N. Y., a corporation of Delaware Application November 7, 1950, Serial No. 194,57 9

12 Claims. (Cl. 95-8) This invention relates to anti-halation layers for photographic materials and particularly to such layers containing an alkali soluble resin.

The present day photographic materials, such as black and white and multilayer color films, have an anti-halation layer interposed between the support and silver halide emulsion layer, as an overcoating over the silver halide emulsion layer when such emulsion is exposed through the support, or as a backing layer, i. e., on the support opposite the silver halide emulsion layer. In order to prevent light scattering or the halation effects caused by reflection of light rays from the support on to the sensitized layer, the general practice in preparing such layers is to disperse or dissolve an anti-halation dye or pigment in a colloidal dispersion of gelatin or in a solution of an alkali soluble resin. In some films, such as motion picture film, the gelatin layer is undesirable not only because of its high coefficient of friction, its low abrasion resistance, and its lack of flexibility, but also because it offsets and blocks readily. Although alkali soluble resins are currently used to replace gelatin and have many advantages over gelatin, i. e., readily soluble in alcohols and in alkaline developers, they too, like gelatin, offset and block readily.

The primary object of the present invention is to provide a new anti-halation layer which will not offset and block.

Other objects and advantages will be apparent by reference to the following description in which its preferred details and embodiments are described.

We have discovered that the addition of a small quantity of a fatty acid amide of from 8 to 18 carbon atoms or mixtures thereof to an alkali soluble resin having dispersed or dissolved therein the usual anti-halation dye or pigment minimizes and, in most instances, precludes the highly undesirable effect of ofiset and blocking, i. e., the separation of'the anti-halation layer from the support and emulsion layer. This separation occurs whenever the film is wound or when the back layer and the emulsion layer are brought into contact with each other by some other means. As a consequence, the silver halide emulsion layer is covered by the offset anti-halation layer which is too difficult to strip off and leads to a film which for all practical purposes must be discarded as useless.

The concentration of the fatty acid amide or mixtures thereof may vary from to 50% of the weight of the alkali soluble resin. Inasmuch as all alkali soluble resins, i. e., those readily soluble in the usual alkaline photographic developing baths, are susceptible to offset and blocking, any one of them may be stabilized against these effects by the addition of the fatty acid amides. Resins of this type'are legion and no difficulty Will be encountered by those practicing this art to select any resin-for a particular film:

As illustrative examples of such resins, the following may be mentioned: The polymerization products of styrene and acrylic acid, vinyl isobutyl ether and maleic acid, vinyl butyl ether and maleic acid, and styrene and maleic acid disclosed in U. S. P. 2,077,789. The condensation products of phenoxyacetic acid and formaldehyde prepared according to the methods disclosed in U. S. P. 2,075,145, 2,089,764, and 2,282,890. The water soluble acid form of cellulose ace'tate-phthalate as described in U. S. P. 1,954,377. The polyvinyl phthalides containing a free carboxylic acid group as disclosed in U..S. P. 2,131,747 and the like.

Alkali soluble resins in which the acid groups are in the form of anhydrides as described in U. S. P. 2,161,788 may be employed. In addition, the copolymers of maleic acid anhydride and styrene, or vinyl butyl ether, vinylisobutyl ether, or vinylethyl ether may also be employed.

The anti-halation dyes or pigments which may be incorporated into the dispersion of the alkali soluble resin are well known and need not be illustrated in detail. However, as a guide, we have found that silver salts of hydroxyazaindolizines, such as 6 [5,7 disulfonaphthalene 1 azo] 7 hydroxy 5 methyl 1,3,4 triazaindolizine, 5 [3,5 dicarboxy phenyl 1 azo] 4- hydroxy-6-methyl-2,3,7-triazaindolizine, and the like, disclosed in U. S. P. 2,390,707; xanthylium dye salts, such as 3,9 dihydroxy 6 p-methoxystyrylxanthylium chloride, 3,9 dihydroxy 6 p diethylaminostyryhtanthylium chloride, 3,9 dihydroxy 6 p dimethylarninostyrylxanthylium chloride, and the like, disclosed in U. S. P. 2,461,485; pyrylium dye salts, such as 4(4-dimethylaminostyryl) 7 hydroxy Z-phenylbenzopyrylium chloride, 2,4 dihydroxy 2 styryl benzopyrylium chloride, 4-hydroxy-2-styrylbenzopyrylium chloride, and the like, as disclosed in U. S. P. 2,461,484; the triphenylmethane derivatives disclosed in U. S. P. 1,912,797, 2,098,891, 2,147,112, 2,150,695, and 2,282,890; the dyestuff combinations disclosed in U. S. P. 1,923,485; the methine and polymethine dyes disclosed in U. S. P. 2,268,798, 2,298,731, and 2,298,733; Prussian blue, titanium dioxide, manganese dioxide, carbon black, and the like, may be employed.

The only prerequisites imposed upon the anti-halation dyes and pigments are that they be readily dischargeable or dispersible in the usual photographic processing baths or optional alkaline pre-baths which may be used for the removal of the resin layer prior to development. As examples of suitable fatty acid amides and mixtures thereof, the following are illustrative:

Caprylamide Capramide Lauramide Myristamide Palmitamide Stearamide Oleamide Oetadecadieneamide The addition of any one or a mixture of the foregoing fatty acid amides not only precludes the undesirable effect of offset and blocking but precludes the formation of calcium or magnesium ions, especially when the processing solutions contain hard water. In our experiments to find suitable agents which would preclude offset and blocking, we have found that gelatin coated with chlorides of fatty acids and gelatin coated with alkali metal salts of fatty acids do not impart these characteristics.

In practicing the present invention, a 0.5 to 5% by weight solution of an alkali soluble resin which is readily soluble in the usual developing agents is dissolved in a lower alkyl alcohol or mixture of such alcohols, such as methanol, ethanol, isopropanol, N- bntanol, and the like. To this solution is then added 0.2 to 4% by weight of an anti-halation dye or pigment. The concentration of fatty acid amide to be added to the dye solution may vary,

as pointed out above, between and 50% based on the weight of the alkali soluble resin.

In the accompanying drawing, the single figure is a sectional view of a photographic film constructed according to our invention. As shown therein, a film base has coated thereon, a layer 11 of a gelatino silver halideemulsion and on the opposite side, an alkali soluble anti-halation layer 12 containing a resin soluble in alkaline photographic processing solutions, an anti-halation dye and a fatty acid amide of from 8 to 18 carbon atoms.

The following examples described in detail the methods for accomplishing the above objects, but it is to be understood that they are merely inserted for the purpose of illustration and are not to be construed as limiting the scope of the invention. The parts given are by weight.

Example I Grams Polyvinyl isobutyl ether-maleic acid anhydride 2.0 Ethanol 48.0 Isopropanol 48.5

3,9 dihydroxy 6-p-methoxystyrylxanthylium chloride 1.5 Stearamide 0.5

The foregoing solution when coated as a backing layer on a base on which was coated the usual silver halide emulsion layer did not separate from the base when the film was wound.

8% palmitarnide 5% stearamide 5% oleamide This solution was coatedin the normal manner as an anti-halation backing of a film base containing the usual gelatino silver halide emulsion layer. When the film was tightly wound and stored for a period of six months, upon unwinding, no offset or adherence of the backing layer to the gelatino silver halide emulsion was noted.

Example III Grams Styrene maleic acid anhydride interpolymer 2.0 Ethanol 60.0 Isopropanol 36.0 Malachite green (C. I. 657) 1.5

Fatty acid amide mixture consisting of:

20% stearamide 60% oleamide 0.5 20% octadecadieneamide When this solution was applied as an anti-halation backing layer in the usual manner, it did not separate from the support nor did it adhere to the emulsion layer when the film was kept Wound for a period of thirty days storage under conditions of elevated temperature and humidity.

It will be understood that the term soluble in alkaline photographic processing solutions as used herein and in the appended claims is intended to include alkaline prebaths. which may be used for the removal of the resin layer prior to development.

We claim:

1. A light sensitive photographic element comprising a support carrying a gelatino silver halide layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, and having dispersed in said backing layer, a fatty acid amide characterized by the following general formula:

RCONI-I2 wherein R represents an aliphatic hydrocarbon chain of from 7 to 17 carbon atoms.

2. A light sensitive photographic element comprising a support carrying a gelatino silver halide layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, said backing layer having caprylamide dispersed therein.

3. A light sensitive photographic element comprising a support carrying a gelatino silver halide layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, said backing layer having lauramide dispersed therein.

4. A light sensitive photographic element comprising a support carrying a gelatino silver halide layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, said backing layer having stearamide dispersed therein.

5. A light sensitive photographic element comprising a support carrying a gelatino silver halide emulsion layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, said backing layer having palmitarnide dispersed therein.

6. A light sensitive photographic element comprising a support carrying a gelatino silver halide emulsion layer, said element having an anti-halation backing layer comprising a resin soluble in alkaline photographic processing solutions, said backing layer having dispersed therein a mixture of stearamide, oleamide, and octadecadieneamide.

7. A photographic element comprising a support carrying a photographic silver-halide emulsion layer and on the opposite side of said support an anti-halation layer comprising a resin soluble in alkaline photographic processing solutions, said anti-halation layer having dispersed therein, a fatty acid amide characterized by the following general formula:

RCONI-Iz wherein R represents an aliphatic hydrocarbon chain of from 7 to 1-7 carbon atoms.

8. A photographic element according to claim 7 Wherein the fatty acid amide is caprylamide.

9. A photographic element according to claim 7 wherein the fatty acid amide is lauramide.

10. A photographic element according to claim 7 wherein the fatty acid amide is stearamide.

11. A photographic element according to claim 7 wherein the fatty acid amide is palmitarnide.

12. A photographic element according to claim 7 containing dispersed in said anti-halation layer, a mixture of stearamide, oleamide and octadecadieneamide.

References Cited in the fileof this patent UNITED STATES PATENTS 2,139,778 Slack et a1. Dec. 13, 1938 2,278,457 Marasco Apr. 7, 1942 2,533,514 Sawdey et a1. Dec. 12, 1950 2,572,988 Collins et a1. Oct. 30, 1951 

1. A LIGHT SENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT CARRYING A GELATINO SILVER HALIDE LAYER, SAID ELEMENT HAVING AN ANTI-HALATION BACKING LAYER COMPRISING A RESIN SOLUBLE IN ALKALINE PHOTOGRAPHIC PROCESSING SOLU- 